CRE 2 Week 10
CRE 2 Week 10
Week 10
1
Topics covered in 2nd half of semester
Week Title
Week 9 Diffusion and reaction
Week 10 Diffusion and reaction
Week 11 Diffusion and reaction
Week 12 Diffusion and reaction
Week 13 Bioreactor
Week 14 Residence time distributions (RTD)
Week 15 Review
Week 16 Final exam
Part 4. Diffusion & Reaction
Content Objectives
➢ Internal effectiveness factor ➢ Understand what the internal
effectiveness factor in a porous
catalyst represents and how it
varies under different conditions
➢ Be able to estimate the value of
effectiveness factor
1st order reaction in spherical catalyst
2 2 1 sinh 𝜙1 𝜆
𝑑 Ψ 2 𝑑Ψ 2 𝑑 𝑦 2
+ − 𝜙1 Ψ = 0 − 𝜙1 𝑦 = 0 Ψ=
𝑑𝜆2 𝜆 𝑑𝜆 𝑑𝜆2 𝜆 sinh 𝜙1
2
𝑑 Ψ 2 cosh 𝜙1 𝜆 𝑧
− 𝜙1 Ψ = 0 Ψ= 𝜆=
𝑑𝜆2 cosh 𝜙1 𝐿
• Instead, what we normally see is that the actual rate of reaction is lower than
expected due to mass transfer limitations.
• To quantify this, we define the internal effectiveness factor of the catalyst (ranging
from 0 to 1) as:
• The value of 𝜂 provides a measure of how far the reactant diffuses into the pellet
before reacting.
• The observed rate, −𝑟𝐴 , is also sometimes given the symbol −𝑟𝐴 (obs)
• The rates of reaction are often expressed in terms of absolute number of moles
converted per unit time:
spherical catalyst
In a spherical catalyst pellet,
4 3
𝑀𝐴𝑠 = 𝑘𝐶𝐴𝑠 × 𝜋𝑅
3
Internal effectiveness factor (𝜂) - order reaction in a1st
spherical catalyst
• The actual rate of reaction is equal to the rate of diffusion of A into the pellet at the
outer surface, as all A going inside the catalyst reacts & no A diffuses back out:
2
𝑀𝐴 = −4𝜋𝑅 𝑊𝐴𝑟 ቚ
𝑟=𝑅
2
𝑑𝐶𝐴
→ 𝑀𝐴 = 4𝜋𝑅 𝐷𝑒 อ
𝑑𝑟
𝑟=𝑅
𝑑Ψ
→ 𝑀𝐴 = 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ቤ
𝑑𝜆 𝜆=1
Internal effectiveness factor (𝜂) for 1
order reaction in
st
a spherical catalyst
• For 1st order reaction
spherical catalyst
Recall that
• So far, we found that 𝑀𝐴 = 4𝜋𝑅𝐷𝑒 𝐶𝐴𝑠 ∅1 coth ∅1 − 1
4 3 𝑘1
𝑀𝐴𝑠 = 𝑘𝐶𝐴𝑠 × 𝜋𝑅 𝜙1 = 𝑅
3 𝐷𝑒
3
• If ∅1 >2 → 𝜂 ≈ 2 ∅1 − 1
∅1
3
• If ∅1 >20 → 𝜂≈
∅1
Influence of catalyst particle geometry on concentration profile and
effectiveness factor for 1 order, isothermal, isobaric reaction
st
𝑘1 𝑘1 𝑘1
Thiele modulus 𝜙1 = 𝑅 𝜙1 = 𝐿 𝜙1 = 𝑅
𝐷𝑒 𝐷𝑒 𝐷𝑒
𝐶𝐴 1 sinh 𝜙1 𝜆 cosh 𝜙1 𝜆 𝐼𝑜 𝜙1 𝜆
Ψ= Ψ= Ψ= Ψ=
𝐶𝐴𝑠 𝜆 sinh 𝜙1 cosh 𝜙1 𝐼𝑜 𝜙1
Note that as ∅1
becomes large, 𝜂 is
independent of
pellet geometry!
Internal effectiveness & Thiele Modulus
2
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝜙𝑛 =
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛
Once in the internal diffusion limited regime, changing factors that affect
the external mass transport rate (eg. fluid velocity) won’t affect the overall
rate of reaction
Actual reaction rate
• For1st order reaction that is limited by internal diffusion
3 3 𝐷𝑒
in spherical catalyst particles, the internal effectiveness 𝜂≈ =
factor (when ∅1 >20) can be approximated as: ∅1 𝑅 𝑘
−𝑟𝐴 = 𝜂(−𝑟𝐴𝑠 )
So, to increase the rate (at a given T),
= 𝜂𝑘𝐶𝐴𝑠 we can:
• Decrease catalyst size
3 3 • Increase the external surface
−𝑟𝐴 = 𝐷𝑒 𝑘𝐶𝐴𝑠 or −𝑟𝐴 = 𝐷𝑒 𝑆𝑎 𝜌𝑐 𝑘"𝐶𝐴𝑠 concentration
𝑅 𝑅
• Increase internal surface area
Internal effectiveness factor (𝜂) for reactions other
than 1 order
st
1/2 1/2
2 3 2 3 𝐷𝑒 (1−𝑛)/2
𝜂= 𝜂= 𝐶𝐴𝑠
𝑛+1 ∅𝑛 𝑛+1 𝑅 𝑘𝑛
Hence, the effectiveness factor decreases with increasing CAs for n > 1
Internal effectiveness factor (𝜂) for reactions with
volume change (𝜀 ≠ 0)
• Effectiveness factor ratios for1 st
Example:
• For a gas phase reaction
A → 2B (𝜀=1)
if Thiele modulus = 10, then
𝜂′Τ𝜂=0.8
Internal effectiveness factor (𝜂)
for exothermic, non-isothermal 1 st
order reactions
• For exothermic, non-isothermal
reactions, it is possible to have 𝜂 > 1,
as the heat generated by reaction
inside the pellet can raise the
temperature above Ts, leading to
faster reaction rates.
3 2
𝜂 = 2 ∅1 coth ∅1 − 1 𝜂∅1 = 3 ∅1 coth ∅1 − 1
∅1
The term on the the LHS is Weisz-Prater parameter, denoted as 𝐶𝑊𝑃
2
𝐶𝑊𝑃 = 𝜂∅1
The Weisz–Prater criterion uses measured values of the observed reaction rate (−𝑟𝐴)
to check whether the reaction is limited by internal diffusion.
Weisz-Prater criterion for internal diffusion
limitations
Internal effectiveness factor and Thiele modulus have already been defined earlier,
as follows: 2 2
2
−𝑟𝐴𝑠 𝑅 −𝑟′𝐴𝑠 𝜌𝑐 𝑅
𝜙1 = =
𝐶𝐴𝑠 𝐷𝑒 𝐶𝐴𝑠 𝐷𝑒
Weisz-Prater parameter (1 st order reaction)
2
𝐶𝑊𝑃 = 𝜂∅1
a) Determine the Thiele modulus and the internal effectiveness factor of the reaction at
320 K. Do these conditions represent a reaction rate controlled or internal diffusion
controlled regime?
b) Calculate the observed rate of reaction at 320 K.
c) If particles of 2 mm diameter are used instead (keeping all other conditions fixed),
how much improvement would we see in the rate of reaction? What would be a
possible downside of making this change?